CN110003781B - Electric heating coating based on multi-level structure graphene and preparation method thereof - Google Patents

Electric heating coating based on multi-level structure graphene and preparation method thereof Download PDF

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CN110003781B
CN110003781B CN201910155113.1A CN201910155113A CN110003781B CN 110003781 B CN110003781 B CN 110003781B CN 201910155113 A CN201910155113 A CN 201910155113A CN 110003781 B CN110003781 B CN 110003781B
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copper
graphene
copper substrate
nanorod array
substrate
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CN110003781A (en
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杜涛
李思幸
吴伟
贺盼盼
其他发明人请求不公开姓名
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Hunan Yijia Zhiene New Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention belongs to the technical field of coatings, and particularly relates to an electrothermal coating based on multi-level structure graphene and a preparation method thereof. The preparation method of the electrothermal coating based on the multilevel-structure graphene comprises the following steps: loading a three-dimensional graphene material on a copper substrate, and then spin-coating a resin film on the surface of the three-dimensional graphene material to obtain the copper substrate/three-dimensional graphene/resin material; corroding the copper substrate of the copper substrate/three-dimensional graphene/resin material to obtain a three-dimensional graphene/resin material; mixing a resin material and an organic solvent, adding the three-dimensional graphene/resin material under a stirring state, and continuously adding a dispersing agent, a flatting agent and a defoaming agent to obtain a mixed solution; grinding the mixed solution to obtain the multilevel-structure graphene-based electrothermal coating; the prepared electric heating coating based on the multi-level structure graphene is uniform in heating, high in heating temperature and strong in adhesive force on an electric heating film.

Description

Electric heating coating based on multi-level structure graphene and preparation method thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an electrothermal coating based on multi-level structure graphene and a preparation method thereof.
Background
The electrothermal film is a film which can generate heat after being electrified, and is usually prepared by coating electrothermal paint on the film and assisting materials such as a metal current-carrying strip, conductive silver paste and the like. The heating principle of the electrothermal film is as follows: under the action of an electric field, molecules in the heating body generate Brownian motion, violent friction and impact occur between the molecules, and the generated heat energy is transmitted outwards in a far infrared radiation mode. As a non-emission energy-saving and environment-friendly heating mode, the electrothermal film is widely applied to the field of heating.
The core heating element of the electric heating film is electric heating paint, and the difference of the performances of the electric heating paint is directly determinedThe quality of the electrothermal film is determined, so that the electrothermal film has higher requirements on the electric conduction and heat conduction performance of the material. The traditional electric heating coating mostly uses carbon powder and graphite as fillers, and usually has the defects of low heating temperature or nonuniform temperature, poor heat resistance and weather resistance and the like. Graphene is a two-dimensional sheet material with a single atomic layer, and has excellent electric and thermal conductivity, and the theoretical electron mobility is about 15000cm2The thermal conductivity of the coating is as high as 5300W/m.K, so that the application of the coating in the aspects of electric conduction and heat conduction is always a hot point of research, and at present, related researches of adding graphene as a filler into an electrothermal coating are carried out, however, the graphene is easy to be subjected to sheet stacking, so that the electrothermal performance of the coating in practical application is far lower than a theoretical value, and if the using amount of the graphene is increased, the adhesion of the coating is reduced, and the service life of the coating is shortened. Therefore, the development of an electrothermal coating with uniform heating and strong adhesive force is needed at present.
Disclosure of Invention
The invention aims to provide an electrothermal coating based on multi-level structure graphene and a preparation method thereof.
In order to achieve the above object, in one aspect, the present invention provides a preparation method of an electrothermal coating based on a multilevel structure graphene, including the following steps:
loading a three-dimensional graphene material on a copper substrate, and then spin-coating a resin film on the surface of the three-dimensional graphene material to obtain the copper substrate/three-dimensional graphene/resin material;
corroding the copper substrate of the copper substrate/three-dimensional graphene/resin material to obtain a three-dimensional graphene/resin material;
mixing a resin material and an organic solvent, adding the three-dimensional graphene/resin material under a stirring state, and continuously adding a dispersing agent, a flatting agent and a defoaming agent to obtain a mixed solution;
and grinding the mixed solution to obtain the multilevel-structure graphene-based electrothermal coating.
Preferably, in the step of mixing the resin material and the organic solvent, adding the three-dimensional graphene/resin material under a stirring state, and continuing to add the dispersing agent, the leveling agent and the defoaming agent to obtain a mixed solution,
the resin material, the three-dimensional graphene/resin material, the dispersing agent, the leveling agent, the defoaming agent and the organic solvent are 50-80 parts by weight: 5-10 parts of: 0.1-5 parts: 0.1-3 parts: 0.1-3 parts: 10-40 parts.
Preferably, the step of loading the three-dimensional graphene material on the copper substrate specifically includes:
vertically growing a copper hydroxide nanorod on a copper substrate by using a chemical oxidation method to obtain a copper substrate/copper hydroxide nanorod array material;
calcining the copper substrate/copper hydroxide nanorod array material in an inert gas atmosphere to obtain a copper substrate/copper oxide nanorod array material;
reducing the copper substrate/copper oxide nanorod array material by using a hydrothermal reduction method to obtain a copper substrate/copper nanorod array material;
and depositing graphene on the copper substrate/copper nanorod array material by using a chemical vapor deposition method to obtain the copper substrate/three-dimensional graphene material.
Preferably, the copper substrate/three-dimensional graphene material comprises a graphene nanotube and a graphene nanosheet, wherein the length of the graphene nanotube is 20-50 nm, and the thickness of the graphene nanosheet is 5-10 nm.
Preferably, before the step of vertically growing the copper hydroxide nanorods on the copper substrate by using the chemical oxidation method, the method further comprises washing the copper substrate with hydrochloric acid and water alternately for several times, wherein the copper substrate is a copper sheet, a copper wire mesh or a copper foam.
Preferably, the step of vertically growing the copper hydroxide nanorods on the copper substrate by using a chemical oxidation method to obtain the copper substrate/copper hydroxide nanorod array material specifically comprises the steps of immersing the copper substrate in a mixed solution of 8-12 mol/L sodium hydroxide solution and 20-30 wt% ammonia water, standing for 1-24 h at room temperature, alternately washing with water and ethanol for several times, and drying to obtain the copper substrate/copper hydroxide nanorod array material; wherein the volume ratio of the sodium hydroxide solution to the ammonia water is 1-3: 1.
preferably, the step of calcining the copper substrate/copper hydroxide nanorod array material in an inert gas atmosphere to obtain the copper substrate/copper oxide nanorod array material specifically comprises calcining the copper substrate/copper hydroxide nanorod array material in an argon atmosphere at 500-600 ℃ for 1-3 h to obtain the copper substrate/copper oxide nanorod array material.
Preferably, the step of reducing the copper substrate/copper oxide nanorod array material by using a hydrothermal reduction method to obtain the copper substrate/copper oxide nanorod array material specifically comprises,
preparing a reducing agent solution from sodium hydroxide, a reducing agent and water;
and adding the copper substrate/copper oxide nanorod array material into the reducing agent solution, carrying out microwave hydrothermal reaction in a microwave reactor at 120-200 ℃ for 0.5-2 h, cooling to room temperature, alternately washing with water and ethanol for several times, and drying to obtain the copper substrate/copper nanorod array material.
Preferably, the reducing agent is one of glucose, hydrazine hydrate, sodium borohydride, ascorbic acid and oxalic acid.
Preferably, the step of depositing graphene on the copper substrate/copper nanorod array material by using a chemical vapor deposition method to obtain the copper substrate/three-dimensional graphene material specifically comprises,
ultrasonically cleaning the copper substrate/copper nanorod array;
placing the copper substrate/copper nanorod array material into a CVD (chemical vapor deposition) tube furnace after ultrasonic cleaning, and heating the CVD tube furnace to 800-1000 ℃ at a heating rate of 5 ℃/min in a mixed atmosphere of hydrogen and argon, wherein the flow rate of hydrogen is 10-30 sccm, and the flow rate of argon is 600-1000 sccm;
adjusting the flow rate of hydrogen to be 80-120 sccm, introducing a carbon source gas, wherein the flow rate of the carbon source gas is 10-50 sccm, and keeping the temperature for 10-20 min, and then turning off the hydrogen and the carbon source gas;
and in an argon atmosphere, cooling the CVD tube furnace to room temperature to obtain the copper substrate/three-dimensional graphene material.
The invention further provides an electrothermal coating based on the multilevel-structure graphene, which is prepared by any preparation method.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, by adding the dispersing agent, the flatting agent, the defoaming agent and the organic solvent, the resin material and the three-dimensional graphene/resin material can be better compounded, and the electric heating coating based on the multi-level structure graphene is provided.
On one hand, the three-dimensional graphene material is loaded on the copper substrate, and is added into a coating formula after being processed by a spin coating process, so that the structural integrity can be ensured to a great extent; on the other hand, the three-dimensional graphene is used as an additive and added into the electrothermal coating, the three-dimensional graphene has a three-dimensional conductive network structure, electrons in the electrothermal coating can freely move along a graphene plane and can also move along the axial direction of the graphene, so that the electric conductivity of the electrothermal coating is excellent; on the other hand, the graphene material has a certain far infrared radiation effect, and can be added into the electrothermal coating to improve the heat conductivity of the electrothermal coating; and the high mechanical strength and chemical inertness of the three-dimensional graphene material also greatly improve the mechanical strength, heat resistance and weather resistance of the electric heating coating.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On one hand, the embodiment of the invention provides a preparation method of an electrothermal coating based on multi-level structure graphene, which comprises the following steps:
s01, loading a three-dimensional graphene material on a copper substrate, and spin-coating a resin film on the surface of the three-dimensional graphene material to obtain the copper substrate/three-dimensional graphene/resin material;
s02, corroding the copper substrate of the copper substrate/three-dimensional graphene/resin material to obtain a three-dimensional graphene/resin material;
s03, mixing a resin material and an organic solvent, adding the three-dimensional graphene/resin material under a stirring state, and continuously adding a dispersing agent, a leveling agent and a defoaming agent to obtain a mixed solution;
and S04, grinding the mixed solution to obtain the multilevel-structure graphene-based electrothermal coating.
According to the embodiment of the invention, the resin material and the three-dimensional graphene/resin material can be better compounded by adding the dispersing agent, the leveling agent, the defoaming agent and the organic solvent, and the electric heating coating based on the multi-level structure graphene.
On one hand, the three-dimensional graphene material is loaded on the copper substrate and added into the coating formula after being processed by the spin coating process, so that the structural integrity can be ensured to a great extent; on the other hand, the three-dimensional graphene is used as an additive and added into the electrothermal coating, the three-dimensional graphene has a three-dimensional conductive network structure, electrons in the electrothermal coating can freely move along a graphene plane and can also move along the axial direction of the graphene, so that the electric conductivity of the electrothermal coating is excellent; on the other hand, the graphene material has a certain far infrared radiation effect, and can be added into the electrothermal coating to improve the heat conductivity of the electrothermal coating; and the high mechanical strength and chemical inertness of the three-dimensional graphene material also greatly improve the mechanical strength, heat resistance and weather resistance of the electric heating coating.
In step S03, the resin material, the three-dimensional graphene/resin material, the dispersant, the leveling agent, the defoaming agent, and the organic solvent are 50 to 80 parts by weight: 5-10 parts of: 0.1-5 parts: 0.1-3 parts: 0.1-3 parts: 10-40 parts. By controlling the proportion of each component in the preparation method, the dispersion uniformity of the three-dimensional graphene/resin material in the resin material can be effectively controlled, so that the electric heating coating based on the multi-level structure graphene is uniform and excellent in electric conduction and heat conduction performance.
In step S01, the step of loading the three-dimensional graphene material on the copper substrate specifically includes:
s011, vertically growing copper hydroxide nanorods on a copper substrate by using a chemical oxidation method to obtain a copper substrate/copper hydroxide nanorod array material;
s012, placing the copper substrate/copper hydroxide nanorod array material in an inert gas atmosphere for calcination to obtain a copper substrate/copper oxide nanorod array material;
s013, reducing the copper substrate/copper oxide nanorod array material by using a hydrothermal reduction method to obtain a copper substrate/copper nanorod array material;
s014, depositing graphene on the copper substrate/copper nanorod array material by using a chemical vapor deposition method to obtain the copper substrate/three-dimensional graphene material.
The method comprises the steps of vertically growing copper hydroxide nanorods on the surface of a copper substrate, reducing the copper hydroxide nanorods into copper nanorods through multiple reduction treatments, depositing graphene on the surfaces of the copper substrate and the copper nanorods, depositing the surface of the copper substrate to obtain a graphene lamellar structure, depositing the surface of the copper nanorods to obtain a graphene tubular structure, wherein the graphene lamellar structure is perpendicular to the graphene tubular structure, the graphene lamellar structure and the graphene tubular structure are manufactured in one step by a chemical vapor deposition method, the deposition thickness is uniform, the graphene lamellar structure and the graphene tubular structure are integrated structures, the two structures are not simply spliced, the phenomena of graphene stacking and agglomeration cannot occur, and the probability of defects of a graphene material is reduced.
And the graphene lamellar structure and the graphene tubular structure form a three-dimensional conductive network system, electrons can freely migrate on the graphene lamellar structure and can also be quickly transferred along the axial direction of the graphene tubular structure, and the conductivity is excellent.
In the embodiment, the graphene with the multi-level structure is deposited on the copper substrate/copper nanorod in one step by a chemical vapor deposition method, so that the obtained copper substrate/three-dimensional graphene material has no stacking phenomenon and excellent conductivity.
The copper substrate/three-dimensional graphene material comprises a graphene nanotube and a graphene nanosheet, wherein the length of the graphene nanotube is 20-50 nm, and the thickness of the graphene nanosheet is 5-10 nm.
Specifically, the graphene tubular structure is a graphene nanotube, the graphene lamellar structure is a graphene nanosheet, the thickness of the graphene nanosheet is 5-10 nm, and the graphene nanosheet is a single-layer graphene nanostructure, so that the stacking phenomenon is further prevented; the length of the graphene nanotube is 20-50 nm, the length of the graphene nanotube is less than 20nm, the length of the graphene nanotube is too short, and the possibility of stacking phenomenon is high; the length of the graphene nanotube is greater than 50nm, and the higher the length of the graphene nanotube is, the higher the possibility that the graphene nanotube is broken or defective is.
Before the step S011, the method further includes washing the copper substrate with hydrochloric acid and water alternately for several times, wherein the copper substrate is a copper sheet, a copper wire mesh or copper foam.
Washing the copper substrate by using hydrochloric acid and water alternately, and cleaning the surface of the copper substrate to remove impurities on the surface of the copper substrate; the concentration of the hydrochloric acid can be 2-5 mol/L.
The step S011 specifically comprises the steps of immersing a copper substrate in a mixed solution of 8-12 mol/L sodium hydroxide solution and 20-30 wt% ammonia water, standing at room temperature for 1-24 hours, alternately washing with water and ethanol for several times, and drying to obtain a copper substrate/copper hydroxide nanorod array material; wherein the volume ratio of the sodium hydroxide solution to the ammonia water is 1-3: 1. wherein, the ethanol can adopt absolute ethanol; the drying may be carried out by air drying.
And S012 specifically comprises the step of calcining the copper substrate/copper hydroxide nanorod array for 1-3 hours at 500-600 ℃ in an argon atmosphere to obtain the copper substrate/copper oxide nanorod array material. Calcining in inert gas atmosphere to prevent other impurity by-products, and the sintered structure is relatively stable.
Step S013 specifically comprises preparing a reducing agent solution from sodium hydroxide, a reducing agent and water;
and adding the copper substrate/copper oxide nanorod array material into the reducing agent solution, carrying out microwave hydrothermal reaction in a microwave reactor at 120-200 ℃ for 0.5-2 h, cooling to room temperature, alternately washing with water and ethanol for several times, and drying to obtain the copper substrate/copper nanorod array material. Through microwave hydrothermal, a reaction system is heated more uniformly, the reaction time is shortened, and the reaction is fully performed through the control of temperature and time.
Preferably, the reducing agent is one of glucose, hydrazine hydrate, sodium borohydride, ascorbic acid and oxalic acid. The raw materials are easy to obtain, and the preparation is more convenient.
Wherein, step S014 specifically includes:
ultrasonically cleaning the copper substrate/copper nanorod array;
placing the copper substrate/copper nanorod array material into a CVD (chemical vapor deposition) tube furnace after ultrasonic cleaning, and heating the CVD tube furnace to 800-1000 ℃ at a heating rate of 5 ℃/min in a mixed atmosphere of hydrogen and argon, wherein the flow rate of hydrogen is 10-30 sccm, and the flow rate of argon is 600-1000 sccm;
adjusting the flow rate of hydrogen to be 80-120 sccm, introducing a carbon source gas, wherein the flow rate of the carbon source gas is 10-50 sccm, and keeping the temperature for 10-20 min, and then turning off the hydrogen and the carbon source gas;
and in an argon atmosphere, cooling the CVD tube furnace to room temperature to obtain the copper substrate/three-dimensional graphene material. The deposited three-dimensional graphene material has uniform film thickness and stable film structure.
Preferably, the carbon source gas is one of methane, ethylene and acetylene; the carbon source gas is easy to obtain and the operation is convenient.
The embodiment of the invention also provides an electrothermal coating based on the multilevel-structure graphene, which is prepared by the preparation method of the electrothermal coating based on the multilevel-structure graphene in any embodiment of the above embodiments.
The electric heating coating based on the multi-level structure graphene is excellent in electric conduction and heat conduction performance.
In the above embodiments, the resin film may be one of a polyurethane resin film, an acrylic resin film, an epoxy resin film, and a silicone resin film;
the resin material can be one of polyurethane resin, acrylic resin, epoxy resin and organic silicon resin;
the dispersant can be HT-5027 of break Thai chemical industry Co., Ltd, Nantong;
the leveling agent may be SN-612 of auxiliary Agents of Nopoptaceae, Japan;
the defoaming agent can be T-7511 of Wang environmental protection science and technology Limited, Guangzhou;
the organic solvent can be one of acetonitrile, dichloromethane, triethylamine, dimethylformamide, carbon tetrachloride, petroleum ether, toluene, xylene, acetone, cyclohexanone and butanol.
The invention is further illustrated by the following specific examples:
example 1
A preparation method of a copper substrate/three-dimensional graphene material comprises the following steps:
s101, washing a copper sheet for multiple times by using 4mol/L hydrochloric acid and water alternately, immersing the washed copper sheet in a mixed solution of 200mL of 10mol/L sodium hydroxide solution and 100mL of 25 wt% ammonia water, and standing for 12h at room temperature; then washing the copper sheet with water and absolute ethyl alcohol for several times respectively, and airing in the air to obtain a copper substrate/copper hydroxide nanorod array material;
s102, calcining the copper substrate/copper hydroxide nanorod array material for 2 hours at 550 ℃ in an argon atmosphere to obtain a copper substrate/copper oxide nanorod array material;
s103, mixing and dissolving 8g of sodium hydroxide and 8g of glucose in 80mL of water, adding the copper substrate/copper oxide nanorod array material into the water, transferring the mixture into a microwave reactor, carrying out microwave hydrothermal reaction for 1h at 160 ℃, cooling to room temperature after the reaction is finished, taking out a solid obtained after the reaction, washing with water and absolute ethyl alcohol for several times respectively, and drying at 60 ℃ for 40min to obtain the copper substrate/copper nanorod array material;
s104, ultrasonically cleaning the copper substrate/copper nanorod array material in water, absolute ethyl alcohol and acetone for 20min in sequence, then placing the copper substrate/copper nanorod array material into a CVD (chemical vapor deposition) tubular furnace, heating the CVD tubular furnace to 1000 ℃ at the speed of 5 ℃/min under the mixed atmosphere of hydrogen with the flow rate of 20sccm and argon with the flow rate of 800sccm, then adjusting the flow rate of the hydrogen to 100sccm, introducing methane gas at the flow rate of 30sccm, keeping the temperature for 15min, turning off the hydrogen and the methane gas, cooling to room temperature in the argon atmosphere, and taking out a sample to obtain the copper substrate/three-dimensional graphene material.
Example 2
A preparation method of a copper substrate/three-dimensional graphene material comprises the following steps:
s201, washing a copper sheet for several times by using 4mol/L hydrochloric acid and water alternately, immersing the washed copper sheet in a mixed solution of 100mL of 10mol/L sodium hydroxide solution and 100mL of 25 wt% ammonia water, and standing for 12h at room temperature; then washing the copper sheet with water and absolute ethyl alcohol for several times respectively, and airing in the air to obtain a copper substrate/copper hydroxide nanorod array material;
s202, calcining the copper substrate/copper hydroxide nanorod array material for 3 hours at 500 ℃ in an argon atmosphere to obtain a copper substrate/copper oxide nanorod array material;
s203, mixing and dissolving 4g of sodium hydroxide and 8g of ascorbic acid in 80mL of water, adding the copper substrate/copper oxide nanorod array material into the water, transferring the mixture into a microwave reactor, carrying out microwave hydrothermal reaction for 2 hours at 120 ℃, cooling to room temperature after the reaction is finished, taking out a solid obtained after the reaction, washing the solid with water and absolute ethyl alcohol for several times respectively, and drying at 50 ℃ for 60min to obtain the copper substrate/copper nanorod array material;
s204, ultrasonically cleaning the copper substrate/copper nanorod array material in water, absolute ethyl alcohol and acetone for 10min in sequence, then placing the copper substrate/copper nanorod array material into a CVD (chemical vapor deposition) tubular furnace, heating the CVD tubular furnace to 800 ℃ at the speed of 5 ℃/min under the mixed atmosphere of hydrogen with the flow rate of 10sccm and argon with the flow rate of 600sccm, then adjusting the flow rate of the hydrogen to 80sccm, introducing ethylene gas at the flow rate of 10sccm, keeping the temperature for 20min, turning off the hydrogen and the ethylene gas, cooling to room temperature in the argon atmosphere, and taking out a sample to obtain the copper substrate/three-dimensional graphene material.
Example 3
A preparation method of a copper substrate/three-dimensional graphene material comprises the following steps:
s301, alternately washing the copper sheet with 4mol/L hydrochloric acid and water for several times, immersing the washed copper sheet in a mixed solution of 300mL of 10mol/L sodium hydroxide solution and 100mL of 25 wt% ammonia water, and standing for 1h at room temperature; then washing the copper sheet with water and absolute ethyl alcohol for several times respectively, and airing in the air to obtain a copper substrate/copper hydroxide nanorod array material;
s302, calcining the copper substrate/copper hydroxide nanorod array material for 1h at 600 ℃ in an argon atmosphere to obtain a copper substrate/copper oxide nanorod array material;
s303, mixing and dissolving 16g of sodium hydroxide and 8g of oxalic acid in 80mL of water, adding the copper substrate/copper oxide nanorod array material, transferring the mixture into a microwave reactor, carrying out microwave hydrothermal reaction at 200 ℃ for 0.5h, cooling to room temperature after the reaction is finished, taking out a solid obtained after the reaction, washing with water and absolute ethyl alcohol for several times respectively, and drying at 80 ℃ for 20min to obtain the copper substrate/copper nanorod array material;
s304, ultrasonically cleaning the copper substrate/copper nanorod array material in water, absolute ethyl alcohol and acetone for 30min in sequence, then placing the copper substrate/copper nanorod array material into a CVD (chemical vapor deposition) tubular furnace, heating the CVD tubular furnace to 900 ℃ at the speed of 5 ℃/min under the mixed atmosphere of hydrogen with the flow rate of 30sccm and argon with the flow rate of 1000sccm, then adjusting the flow rate of the hydrogen to 120sccm, introducing acetylene gas at the flow rate of 50sccm, keeping the temperature for 10min, turning off the hydrogen and the acetylene gas, cooling to room temperature in the argon atmosphere, and taking out a sample to obtain the copper substrate/three-dimensional graphene material.
Example 4
S401, spin-coating a polyurethane resin film on the surface of the copper substrate/three-dimensional graphene material prepared in the embodiment 1 by using a spin coater, then placing the copper substrate/three-dimensional graphene material on a heating table, heating the copper substrate/three-dimensional graphene material at 100 ℃ for 10min, immersing the heated copper substrate/three-dimensional graphene material in 0.5mol/L ferric chloride solution, standing the copper substrate/three-dimensional graphene material for two days, centrifuging the copper substrate/three-dimensional graphene material after the copper substrate is corroded and disappears, washing the copper substrate/three-dimensional graphene material with water for several times, and drying;
s402, uniformly mixing 500g of polyurethane resin and 44.6g of dimethylformamide, adding 5g of the polyurethane resin/three-dimensional graphene composite material obtained in the step S401 under a stirring state, continuously stirring for 2 hours, then adding 1g of dispersing agent, 0.2g of flatting agent and 0.2g of defoaming agent, and uniformly stirring to obtain a mixed solution;
and S403, placing the mixed solution into a ball mill for ball milling, wherein the ball milling speed is 600r/min, and the ball milling time is 2 hours, so that the electric heating coating based on the multilevel-structure graphene is obtained.
Example 5
S501, spin-coating an acrylic resin film on the surface of the copper substrate/three-dimensional graphene material prepared in the embodiment 2 by using a spin coater, then placing the copper substrate/three-dimensional graphene material on a heating table, heating the copper substrate/three-dimensional graphene material at 80 ℃ for 20min, immersing the heated copper substrate/three-dimensional graphene material in 1mol/L ferric chloride solution, standing the copper substrate/three-dimensional graphene material for two days, centrifuging the copper substrate/three-dimensional graphene material after the copper substrate is corroded and disappears, washing the copper substrate/three-dimensional graphene material with water for several times;
s502, uniformly mixing 600g of acrylic resin and 31g of petroleum ether, adding 6g of the acrylic resin/three-dimensional graphene composite material obtained in the step S501 in a stirring state, continuously stirring for 1.5h, then adding 2g of a dispersing agent, 0.5g of a leveling agent and 0.5g of a defoaming agent, and uniformly stirring to obtain a mixed solution;
s503, placing the mixed solution in a ball mill for ball milling, wherein the ball milling speed is 650r/min, and the ball milling time is 1.5h, so that the electric heating coating based on the multilevel-structure graphene is obtained.
Example 6
S601, spin-coating an epoxy resin film on the surface of the copper substrate/three-dimensional graphene material prepared in the embodiment 3 by using a spin coater, then placing the copper substrate/three-dimensional graphene material on a heating table, heating the copper substrate/three-dimensional graphene material at 90 ℃ for 15min, immersing the heated copper substrate/three-dimensional graphene material in 0.8mol/L ferric chloride solution, standing the copper substrate/three-dimensional graphene material for two days, centrifuging the copper substrate/three-dimensional graphene material after the copper substrate is corroded and disappears, washing the copper substrate/three-dimensional graphene material with water for several times;
s602, uniformly mixing 650g of epoxy resin and 23g of xylene, adding 6g of the epoxy resin/three-dimensional graphene composite material obtained in the step S601 under a stirring state, continuously stirring for 1h, then adding 3g of a dispersing agent, 1g of a leveling agent and 1g of a defoaming agent, and uniformly stirring to obtain a mixed solution;
and S603, placing the mixed solution into a ball mill for ball milling, wherein the ball milling speed is 700r/min, and the ball milling time is 1h, so that the electric heating coating based on the multilevel-structure graphene is obtained.
Example 7
S701, spin-coating an organic silicon resin film on the surface of the copper substrate/three-dimensional graphene material prepared in the embodiment 3 by using a spin coater, then placing the copper substrate/three-dimensional graphene material on a heating table, heating the copper substrate/three-dimensional graphene material at 120 ℃ for 5min, immersing the heated copper substrate/three-dimensional graphene material in 0.1mol/L ferric chloride solution, standing the heated copper substrate/three-dimensional graphene material for two days, centrifuging the heated copper substrate/three-dimensional graphene material after the copper substrate is corroded and disappears, washing the copper substrate/three-dimensional graphene material with water;
s702, uniformly mixing 700g of organic silicon resin and 14g of water, adding 8g of the organic silicon resin/three-dimensional graphene composite material obtained in the step S701 in a stirring state, continuously stirring for 2 hours, adding 4g of a dispersing agent, 2g of a flatting agent and 2g of a defoaming agent, and uniformly stirring to obtain a mixed solution;
and S703, placing the mixed solution into a ball mill for ball milling, wherein the ball milling speed is 800r/min, and the ball milling time is 0.5h, so that the electric heating coating based on the multilevel-structure graphene is obtained.
Comparative example 1
Different from the embodiment 3, the two-dimensional graphene sheet is deposited on the surface of the copper sheet by CVD, and the CVD deposition comprises the following specific steps: the copper sheet is sequentially subjected to ultrasonic cleaning in water, absolute ethyl alcohol and acetone for 30min, then the copper sheet is placed into a CVD (chemical vapor deposition) tubular furnace, the CVD tubular furnace is heated to 900 ℃ at the speed of 5 ℃/min under the mixed atmosphere of hydrogen with the flow rate of 30sccm and argon with the flow rate of 1000sccm, then the flow rate of the hydrogen is adjusted to 120sccm, acetylene gas is introduced at the flow rate of 50sccm, the heat is preserved for 10min, the hydrogen and the acetylene gas are turned off, the temperature is reduced to the room temperature in the argon atmosphere, and a sample is taken out to obtain the copper substrate/two-dimensional graphene material.
S801, spin-coating a polyurethane resin film on the surface of a copper substrate/two-dimensional graphene material by using a spin coater, then placing the copper substrate/two-dimensional graphene material on a heating table, heating the copper substrate/two-dimensional graphene material at 100 ℃ for 10min, immersing the heated copper substrate/two-dimensional graphene material into 0.5mol/L ferric chloride solution, standing the copper substrate/two-dimensional graphene material for two days, centrifuging the copper substrate/two-dimensional graphene material after the copper substrate is corroded and disappears, washing the copper substrate/two-dimensional graphene material with water for several times, and drying;
s802, uniformly mixing 500g of polyurethane resin and 44.6g of dimethylformamide, adding 5g of the polyurethane resin/two-dimensional graphene composite material obtained in the step S801 under a stirring state, continuously stirring for 2 hours, then adding 1g of dispersing agent, 0.2g of flatting agent and 0.2g of defoaming agent, and uniformly stirring to obtain a mixed solution;
and S803, placing the mixed solution in a ball mill for ball milling, wherein the ball milling speed is 600r/min, and the ball milling time is 2h, so that the two-dimensional graphene-based electrothermal coating is obtained.
And (3) testing the electric heating performance:
the electrothermal coatings based on the multi-level structure graphene prepared in examples 4 to 7 and the electrothermal coating based on the two-dimensional graphene prepared in comparative example 1 were applied to the surface of the substrate by using coaters, respectively, and then dried at 100 ℃.
The electric-heat conversion efficiency is measured by adopting a detection method in a JG/T286-:
Figure BDA0001982653720000121
Figure BDA0001982653720000131
the table shows that the electrothermal conversion efficiency of the electrothermal coating based on the multilevel-structure graphene is over 98 percent, which is obviously higher than that of the electrothermal coating taking the traditional two-dimensional graphene as an additive, and the electrothermal coating based on the multilevel-structure graphene prepared by the invention has excellent electrothermal performance.
The present invention has been described in further detail with reference to the specific embodiments thereof, and it should be understood that the foregoing is only illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, but rather that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.

Claims (9)

1. A preparation method of an electrothermal coating based on multilevel-structure graphene is characterized by comprising the following steps:
loading a three-dimensional graphene material on a copper substrate, and then spin-coating a resin film on the surface of the three-dimensional graphene material to obtain the copper substrate/three-dimensional graphene/resin material; the method specifically comprises the following steps of loading the three-dimensional graphene material on the copper substrate: vertically growing a copper hydroxide nanorod on a copper substrate by using a chemical oxidation method to obtain a copper substrate/copper hydroxide nanorod array material; calcining the copper substrate/copper hydroxide nanorod array material in an inert gas atmosphere to obtain a copper substrate/copper oxide nanorod array material; reducing the copper substrate/copper oxide nanorod array material by using a hydrothermal reduction method to obtain a copper substrate/copper nanorod array material; depositing graphene on the copper substrate/copper nanorod array material by using a chemical vapor deposition method to obtain a copper substrate/three-dimensional graphene material;
corroding the copper substrate of the copper substrate/three-dimensional graphene/resin material to obtain a three-dimensional graphene/resin material;
mixing a resin material and an organic solvent, adding the three-dimensional graphene/resin material under a stirring state, and continuously adding a dispersing agent, a flatting agent and a defoaming agent to obtain a mixed solution;
and grinding the mixed solution to obtain the multilevel-structure graphene-based electrothermal coating.
2. The method for preparing an electrothermal coating based on multilevel structure graphene according to claim 1, wherein in the step of mixing a resin material and an organic solvent, adding the three-dimensional graphene/resin material under stirring, and further adding a dispersant, a leveling agent, and a defoaming agent to obtain a mixed solution,
the resin material, the three-dimensional graphene/resin material, the dispersing agent, the leveling agent, the defoaming agent and the organic solvent are 50-80 parts by weight: 5-10 parts of: 0.1-5 parts: 0.1-3 parts: 0.1-3 parts: 10-40 parts.
3. The preparation method of the multilevel-structure-graphene-based electrothermal paint according to claim 1, wherein the copper-based/three-dimensional graphene material comprises graphene nanotubes and graphene nanoplatelets, the length of the graphene nanotubes is 20-50 nm, and the thickness of the graphene nanoplatelets is 5-10 nm.
4. The method of preparing an electrothermal coating based on multilevel structure graphene according to claim 1, further comprising, before the step of vertically growing the copper hydroxide nanorods on the copper substrate using a chemical oxidation method, washing the copper substrate with hydrochloric acid and water alternately several times, wherein the copper substrate is a copper sheet, a copper wire mesh or a copper foam.
5. The preparation method of the multilevel-structure-graphene-based electrothermal coating material according to claim 1, wherein the step of vertically growing the copper hydroxide nanorods on the copper substrate by using a chemical oxidation method to obtain the copper substrate/copper hydroxide nanorod array material specifically comprises the steps of immersing the copper substrate in a mixed solution of 8-12 mol/L sodium hydroxide solution and 20-30 wt% ammonia water, standing at room temperature for 1-24 h, alternately washing with water and ethanol for several times, and drying to obtain the copper substrate/copper hydroxide nanorod array material; wherein the volume ratio of the sodium hydroxide solution to the ammonia water is 1-3: 1.
6. the preparation method of the multilevel-structure-graphene-based electrothermal coating according to claim 1, wherein the step of calcining the copper substrate/copper hydroxide nanorod array material in an inert gas atmosphere to obtain the copper substrate/copper oxide nanorod array material specifically comprises the step of calcining the copper substrate/copper hydroxide nanorod array material in an argon atmosphere at 500-600 ℃ for 1-3 h to obtain the copper substrate/copper oxide nanorod array material.
7. The method for preparing an electrothermal coating based on multilevel structure graphene according to claim 1, wherein the step of reducing the copper substrate/copper oxide nanorod array material by a hydrothermal reduction method to obtain the copper substrate/copper nanorod array material specifically comprises,
preparing a reducing agent solution from sodium hydroxide, a reducing agent and water;
and adding the copper substrate/copper oxide nanorod array material into the reducing agent solution, carrying out microwave hydrothermal reaction in a microwave reactor at 120-200 ℃ for 0.5-2 h, cooling to room temperature, alternately washing with water and ethanol for several times, and drying to obtain the copper substrate/copper nanorod array material.
8. The method for preparing an electrothermal coating based on multilevel structure graphene according to claim 1, wherein the step of depositing graphene on the copper substrate/copper nanorod array material by using chemical vapor deposition to obtain a copper substrate/three-dimensional graphene material specifically comprises,
ultrasonically cleaning the copper substrate/copper nanorod array;
placing the copper substrate/copper nanorod array material into a CVD (chemical vapor deposition) tube furnace after ultrasonic cleaning, and heating the CVD tube furnace to 800-1000 ℃ at a heating rate of 5 ℃/min in a mixed atmosphere of hydrogen and argon, wherein the flow rate of hydrogen is 10-30 sccm, and the flow rate of argon is 600-1000 sccm;
adjusting the flow rate of hydrogen to be 80-120 sccm, introducing a carbon source gas, wherein the flow rate of the carbon source gas is 10-50 sccm, and keeping the temperature for 10-20 min, and then turning off the hydrogen and the carbon source gas;
and in an argon atmosphere, cooling the CVD tube furnace to room temperature to obtain the copper substrate/three-dimensional graphene material.
9. An electrothermal coating based on multilevel structure graphene, which is characterized in that the multilevel structure graphene is prepared by the preparation method of the electrothermal coating based on multilevel structure graphene according to any claim 1-8.
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